CN114214031B - Flame-retardant polyphenyl ether adhesive, and preparation method and application thereof - Google Patents
Flame-retardant polyphenyl ether adhesive, and preparation method and application thereof Download PDFInfo
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J187/00—Adhesives based on unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
- C09J187/005—Block or graft polymers not provided for in groups C09J101/00 - C09J185/04
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- C08L2201/02—Flame or fire retardant/resistant
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Abstract
The invention provides a flame-retardant polyphenyl ether adhesive, a preparation method and application thereof, wherein the flame-retardant polyphenyl ether adhesive is formed by mixing 100 parts by mass of low-molecular-weight epoxidized phosphorus-containing polyphenyl ether, 30-100 parts by mass of epoxy resin, 10-30 parts by mass of epoxy resin curing agent and 50-100 organic solvents. Wherein, the preparation process of the low molecular weight epoxidized phosphorus-containing polyphenyl ether is as follows: hexachlorotriphosphazene and bisphenol A are subjected to nucleophilic substitution reaction to synthesize a phosphorus-containing bisphenol compound, then the phosphorus-containing bisphenol compound, polyphenyl ether and a free radical initiator are reacted to obtain low-molecular-weight polyphenyl ether, and finally the low-molecular-weight polyphenyl ether is further subjected to epoxy group addition reaction with an epoxy compound to obtain the low-molecular-weight epoxidized phosphorus-containing polyphenyl ether. The polyphenyl ether adhesive has excellent dielectric property and processability, and the flame retardant property of the polyphenyl ether adhesive is further improved.
Description
Technical Field
The invention relates to the field of adhesives, in particular to an adhesive composition of low-molecular-weight epoxidized phosphorus-containing polyphenyl ether, epoxy resin, an epoxy resin curing agent and an organic solvent.
Background
The copper-clad plate is an upstream substrate of the printed circuit board, has the functions of supporting, conducting and insulating, has great influence on energy loss, transmission speed, characteristic resistance and the like of signals in a circuit, and is an important basic material in the electronic industry. The resin substrate is a key factor for determining the performance of the copper-clad plate, and along with the continuous development of electronic products, the traditional epoxy resin substrate can not meet the technical development requirements of electronic industry products, so that the polymer substrate for developing the copper-clad plate with low dielectric constant, low dielectric loss and high heat resistance becomes a hot spot for research of the copper-clad plate.
The polyphenyl ether contains a large number of benzene ring structures in the molecule, has no strong polar groups, has higher hardness and toughness and excellent resistance, and simultaneously has low dielectric constant and dielectric loss, thereby becoming the preferred matrix resin of the high-performance copper-clad plate gradually. However, conventional polyphenylene ethers have disadvantages of large melt viscosity, poor fluidity, low glass transition temperature, etc., and generally have a method of decreasing the molecular weight of the polyphenylene ether to increase compatibility with epoxy resins and further undergo chemical crosslinking at a later stage.
From the prior researches, the developed polyphenyl ether matrix resin of the copper-clad plate solves the problems of dielectric constant, machining performance and the like, but the electronic industry products can generate a certain amount of heat during the working process, so that the flame retardant property of the matrix resin of the copper-clad plate needs to be further enhanced. In recent years, the frequent occurrence of fire causes great harm to the life safety and property safety of human beings, and the fields of electronic devices and the like have increasingly severe fire resistance grades for materials, so that how to improve the fire resistance of matrix resin for copper-clad plates is a key problem to be solved at present.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and provides a flame-retardant polyphenyl ether adhesive and a preparation method thereof, which obviously improve the flame retardant property of the polyphenyl ether adhesive on the premise of ensuring the dielectric property and the processability of the adhesive.
The aim of the invention is realized by the following technical scheme: hexachloro-tripolyphosphazene and bisphenol A are subjected to nucleophilic substitution reaction to synthesize a phosphorus-containing bisphenol compound, then the phosphorus-containing bisphenol compound, polyphenyl ether and a free radical initiator are reacted to obtain low-molecular-weight polyphenyl ether, then the low-molecular-weight polyphenyl ether is further subjected to epoxy group addition reaction with an epoxy compound to obtain low-molecular-weight epoxidized phosphorus-containing polyphenyl ether, and finally the low-molecular-weight epoxidized phosphorus-containing polyphenyl ether, epoxy resin, an epoxy resin curing agent and an organic solvent are uniformly mixed to obtain the flame-retardant polyphenyl ether adhesive. The polyphenyl ether adhesive has excellent dielectric property and processability, and the flame retardant property of the polyphenyl ether adhesive is further improved.
A flame-retardant polyphenyl ether adhesive and a preparation method thereof comprise the following steps:
s1, preparing a phosphorus-containing bisphenol compound;
mixing bisphenol A, triethylamine and tetrahydrofuran, dropwise adding hexachloro-triphosphazene dissolved in tetrahydrofuran after uniform stirring, dropwise adding triethylamine and methanol dissolved in tetrahydrofuran for continuous reaction after stirring reaction, filtering to obtain a crude product, and extracting and removing impurities from the crude product to obtain a phosphorus-containing bisphenol compound;
specifically, bisphenol A, triethylamine and tetrahydrofuran are added into a round-bottom flask and stirred uniformly, then hexachlorophosphazene dissolved in tetrahydrofuran is dripped into the round-bottom flask, stirred and reacted for 8-24 hours at 25 ℃, then triethylamine and methanol dissolved in tetrahydrofuran are dripped into the round-bottom flask and reacted for 8-24 hours continuously, the reaction solution is filtered to obtain filtrate, the solvent is removed by reduced pressure distillation, the crude product is dissolved in chloroform, the impurity is removed by saturated sodium chloride solution extraction at room temperature, and then the chloroform in the oil phase is removed by reduced pressure distillation, thus obtaining the phosphorus-containing bisphenol compound; wherein, the mol ratio of hexachlorotriphosphazene, bisphenol A, triethylamine, methanol and triethylamine is 1:2:2:4:4, the total mass part ratio of tetrahydrofuran to hexachlorotriphosphazene, bisphenol A, triethylamine, methanol and triethylamine is 10-50: 1.
s2, preparing low molecular weight polyphenyl ether;
adding polyphenyl ether, phosphorus-containing bisphenol compound and mesitylene into an autoclave, heating to 80-100 ℃ and stirring for dissolution, then adding a free radical initiator for reaction, and washing and removing mesitylene from the reaction liquid after the reaction to prepare low-molecular-weight polyphenyl ether;
specifically, adding polyphenyl ether, phosphorus-containing bisphenol compound and mesitylene into an autoclave, heating to 80-100 ℃ and stirring for dissolution, adding a free radical initiator dissolved in mesitylene into the autoclave within 1-6 h, continuing to react for 1-6 h, washing the reaction solution with sodium bicarbonate aqueous solution, and removing mesitylene in an oil phase through reduced pressure distillation to obtain low molecular weight polyphenyl ether; wherein the mass ratio of the polyphenyl ether, the phosphorus-containing bisphenol compound, the free radical initiator and the mesitylene is 1:0.1 to 0.3:0.02 to 0.05:3 to 5.
S3, preparing low molecular weight epoxidized phosphorus-containing polyphenyl ether;
mixing low molecular weight polyphenyl ether, an epoxy compound, a catalyst and mesitylene for high-temperature reaction to obtain low molecular weight epoxidized phosphorus-containing polyphenyl ether;
specifically, adding low molecular weight polyphenyl ether, an epoxy compound, a catalyst and mesitylene into a reactor, heating to 100-150 ℃ to react for 2-12 h, and distilling under reduced pressure to remove a solvent to obtain low molecular weight epoxidized phosphorus-containing polyphenyl ether; wherein the mass portion ratio of the low molecular weight polyphenyl ether, the epoxy compound, the catalyst and the mesitylene is 1:0.2 to 0.8:0.001 to 0.01:3 to 5.
S4, uniformly mixing the low molecular weight epoxidized phosphorus-containing polyphenyl ether, epoxy resin, an epoxy resin curing agent and an organic solvent C to obtain the flame-retardant polyphenyl ether adhesive.
Specifically, 100 parts by mass of low molecular weight epoxidized phosphorus-containing polyphenyl ether, 30-100 parts by mass of epoxy resin, 10-30 parts by mass of epoxy resin curing agent and 50-100 organic solvent C are uniformly mixed, and the flame-retardant polyphenyl ether adhesive is obtained.
Preferably, the free radical initiator is one or more of di-tert-butyl phthalate peroxide, tert-butyl hydroperoxide, benzoyl peroxide, dicumyl peroxide, lauroyl peroxide and di-tert-butyl peroxide.
Preferably, the epoxy compound is one or more of bisphenol a type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, alicyclic epoxy resin and biphenyl type epoxy resin.
Preferably, the catalyst is one or more of tetrabutylammonium chloride, tetramethyl ammonium bromide, tetraphenyl phosphine bromide, amyl triphenyl phosphine bromide and 2-methylimidazole.
Preferably, the epoxy resin is one or more of tetraglycidyl diamino diphenyl methane, N, N, N' -tetraglycidyl meta-xylene diamine, triglycidyl para-aminophenol, tetraglycidyl bisaminomethyl cyclohexanone, phenol novolac type epoxy resin and cresol novolac type epoxy resin.
Preferably, the epoxy resin curing agent is one or more of dicyandiamide, diaminodiphenyl methane, triethylamine and m-phenylenediamine.
Preferably, the organic solvent C is one or more of toluene, xylene, acetone and butanone.
The beneficial effects of the invention are as follows:
1. the flame-retardant polyphenyl ether adhesive disclosed by the invention comprises low-molecular-weight epoxidized phosphorus-containing polyphenyl ether, epoxy resin, an epoxy resin curing agent and an organic solvent, has excellent dielectric property and processability, and meanwhile, the flame retardant property of the polyphenyl ether adhesive is further improved.
2. The flame-retardant polyphenyl ether adhesive disclosed by the invention is simple and easy to control in preparation process, low in production cost and easy for industrial production.
Detailed Description
The technical scheme of the present invention is described in further detail below, but the scope of the present invention is not limited to the following.
Number average molecular weight (M) w ) Is determined by: the weight average molecular weight of the polyphenylene ether was determined by gel chromatography using polystyrene as a standard substance and chloroform as a mobile phase at 40℃and a detector as a photodiode array detector (254 nm wavelength).
Limiting oxygen index test: measuring by using a Atlas Limiting Oxygen Index instrument, taking liquefied petroleum gas as an ignition source, solidifying and forming the polyphenyl ether adhesive, and measuring the sample size: 125 mm. Times.10 mm. Times.2 mm.
Example 1
A flame-retardant polyphenyl ether adhesive and a preparation method thereof comprise the following steps:
s1, adding 2mol of bisphenol A, 2mol of triethylamine and 15.4Kg of tetrahydrofuran into a round-bottom flask, uniformly stirring, then dropwise adding 1mol of hexachlorotriphosphazene dissolved in the tetrahydrofuran into the round-bottom flask, stirring at 25 ℃ for reaction for 24 hours, then dropwise adding 4mol of triethylamine and 4mol of methanol dissolved in the tetrahydrofuran into the round-bottom flask, continuing to react for 24 hours, filtering the reaction solution to obtain a filtrate, distilling under reduced pressure to remove a solvent, dissolving a crude product in chloroform, extracting with saturated sodium chloride solution at room temperature to remove impurities, and distilling under reduced pressure to remove chloroform in an oil phase to obtain a phosphorus-containing bisphenol compound;
s2, adding 10Kg of polyphenyl ether, 2Kg of phosphorus-containing bisphenol compound and 30Kg of mesitylene into an autoclave, heating to 90 ℃ and stirring for dissolution, adding 0.3Kg of di-tert-butyl phthalate peroxide dissolved in the mesitylene into the autoclave within 3 hours, continuing to react for 4 hours, washing the reaction solution with sodium bicarbonate aqueous solution, and removing the mesitylene in the oil phase through reduced pressure distillation to obtain low molecular weight polyphenyl ether (the number average molecular weight is 3080);
s3, adding 10Kg of low molecular weight polyphenyl ether, 2Kg of bisphenol A epoxy resin, 0.05Kg of tetrabutylammonium chloride and 30Kg of mesitylene into a reactor, heating to 130 ℃ for reaction for 6 hours, and distilling under reduced pressure to remove a solvent to obtain low molecular weight epoxidized phosphorus-containing polyphenyl ether;
s4, uniformly mixing 100Kg of low molecular weight epoxidized phosphorus-containing polyphenyl ether, 30Kg of tetraglycidyl diamino diphenyl methane, 10Kg of dicyandiamide and 50Kg of toluene to obtain the flame-retardant polyphenyl ether adhesive.
Comparative example
S1, adding 10Kg of polyphenyl ether, 2Kg of bisphenol A and 30Kg of mesitylene into an autoclave, heating to 90 ℃ and stirring for dissolution, adding 0.3Kg of di-tert-butyl phthalate peroxide dissolved in the mesitylene into the autoclave within 3 hours, continuing to react for 4 hours, washing the reaction solution with sodium bicarbonate aqueous solution, and removing the mesitylene in the oil phase through reduced pressure distillation to obtain low molecular weight polyphenyl ether (the number average molecular weight is 2970);
s2, adding 10Kg of low molecular weight polyphenyl ether, 2Kg of bisphenol A epoxy resin, 0.05Kg of tetrabutylammonium chloride and 30Kg of mesitylene into a reactor, heating to 130 ℃ for reaction for 6 hours, and distilling under reduced pressure to remove a solvent to obtain low molecular weight epoxidized phosphorus-containing polyphenyl ether;
s3, uniformly mixing 100Kg of low molecular weight epoxidized phosphorus-containing polyphenyl ether, 30Kg of tetraglycidyl diamino diphenyl methane, 10Kg of dicyandiamide and 50Kg of toluene to obtain the common polyphenyl ether adhesive.
Example 2
A flame-retardant polyphenyl ether adhesive and a preparation method thereof comprise the following steps:
s1, adding 2mol of bisphenol A, 2mol of triethylamine and 77Kg of tetrahydrofuran into a round-bottom flask, uniformly stirring, then dropwise adding 1mol of hexachlorotriphosphazene dissolved in the tetrahydrofuran into the round-bottom flask, stirring at 25 ℃ for reaction for 8 hours, then dropwise adding 4mol of triethylamine and 4mol of methanol dissolved in the tetrahydrofuran into the round-bottom flask, continuing to react for 8 hours, filtering the reaction solution to obtain a filtrate, distilling under reduced pressure to remove a solvent, dissolving a crude product in chloroform, extracting with a saturated sodium chloride solution at room temperature to remove impurities, and distilling under reduced pressure to remove chloroform in an oil phase to obtain a phosphorus-containing bisphenol compound;
s2, adding 10Kg of polyphenyl ether, 1Kg of phosphorus-containing bisphenol compound and 50Kg of mesitylene into an autoclave, heating to 80 ℃ and stirring for dissolution, adding 0.2Kg of tertiary butyl hydroperoxide dissolved in the mesitylene into the reaction kettle within 1h, continuing to react for 6h, washing the reaction solution with sodium bicarbonate aqueous solution, and removing the mesitylene in the oil phase through reduced pressure distillation to obtain the low molecular weight polyphenyl ether;
s3, adding 10Kg of low molecular weight polyphenyl ether, 8Kg of bisphenol F type epoxy resin, 0.1Kg of tetrabutylammonium bromide and 50Kg of mesitylene into a reactor, heating to 150 ℃ for reaction for 2 hours, and distilling under reduced pressure to remove a solvent to obtain low molecular weight epoxidized phosphorus-containing polyphenyl ether;
s4, uniformly mixing 100Kg of low molecular weight epoxidized phosphorus-containing polyphenyl ether, 100Kg of N, N' -tetraglycidyl m-xylylenediamine, 30Kg of diaminodiphenylmethane and 100Kg of xylene to obtain the flame-retardant polyphenyl ether adhesive.
Example 3
A flame-retardant polyphenyl ether adhesive and a preparation method thereof comprise the following steps:
s1, adding 2mol of bisphenol A, 2mol of triethylamine and 50Kg of tetrahydrofuran into a round-bottom flask, uniformly stirring, then dropwise adding 1mol of hexachlorotriphosphazene dissolved in the tetrahydrofuran into the round-bottom flask, stirring at 25 ℃ for reaction for 24 hours, then dropwise adding 4mol of triethylamine and 4mol of methanol dissolved in the tetrahydrofuran into the round-bottom flask, continuing to react for 24 hours, filtering the reaction solution to obtain a filtrate, distilling under reduced pressure to remove a solvent, dissolving a crude product in chloroform, extracting with a saturated sodium chloride solution at room temperature to remove impurities, and distilling under reduced pressure to remove chloroform in an oil phase to obtain a phosphorus-containing bisphenol compound;
s2, adding 10Kg of polyphenyl ether, 2Kg of phosphorus-containing bisphenol compound and 40Kg of mesitylene into an autoclave, heating to 100 ℃ and stirring for dissolution, adding 0.2Kg of benzoyl peroxide dissolved in the mesitylene into the reaction kettle within 6 hours, continuing to react for 1 hour, washing the reaction solution with sodium bicarbonate aqueous solution, and removing the mesitylene in the oil phase through reduced pressure distillation to obtain the low molecular weight polyphenyl ether;
s3, adding 10Kg of low molecular weight polyphenyl ether, 5Kg of bisphenol S type epoxy resin, 0.06Kg of tetraphenyl phosphine bromide and 40Kg of mesitylene into a reactor, heating to 100 ℃ for reaction for 12 hours, and distilling under reduced pressure to remove a solvent to obtain low molecular weight epoxidized phosphorus-containing polyphenyl ether;
s4, uniformly mixing 100Kg of low molecular weight epoxidized phosphorus-containing polyphenyl ether, 60Kg of triglycidyl para-aminophenol, 20Kg of triethylamine and 50Kg of acetone to obtain the flame-retardant polyphenyl ether adhesive.
Example 4
A flame-retardant polyphenyl ether adhesive and a preparation method thereof comprise the following steps:
s1, adding 2mol of bisphenol A, 2mol of triethylamine and 40Kg of tetrahydrofuran into a round-bottom flask, uniformly stirring, then dropwise adding 1mol of hexachlorotriphosphazene dissolved in the tetrahydrofuran into the round-bottom flask, stirring at 25 ℃ for reaction for 16 hours, then dropwise adding 4mol of triethylamine and 4mol of methanol dissolved in the tetrahydrofuran into the round-bottom flask, continuing to react for 16 hours, filtering the reaction solution to obtain a filtrate, distilling under reduced pressure to remove a solvent, dissolving a crude product in chloroform, extracting with a saturated sodium chloride solution at room temperature to remove impurities, and distilling under reduced pressure to remove chloroform in an oil phase to obtain a phosphorus-containing bisphenol compound;
s2, adding 10Kg of polyphenyl ether, 2.5Kg of phosphorus-containing bisphenol compound and 50Kg of mesitylene into an autoclave, heating to 120 ℃ and stirring for dissolution, adding 0.4Kg of lauroyl peroxide dissolved in the mesitylene into the reaction kettle within 4 hours, continuing to react for 4 hours, washing the reaction solution with sodium bicarbonate aqueous solution, and removing the mesitylene in the oil phase through reduced pressure distillation to obtain the low molecular weight polyphenyl ether;
s3, adding 10Kg of low molecular weight polyphenyl ether, 4Kg of alicyclic epoxy resin, 0.04Kg of amyl triphenylphosphine bromide and 50Kg of mesitylene into a reactor, heating to 150 ℃ for reaction for 2 hours, and distilling under reduced pressure to remove a solvent to obtain low molecular weight epoxidized phosphorus-containing polyphenyl ether;
s4, uniformly mixing 100Kg of low molecular weight epoxidized phosphorus-containing polyphenyl ether, 40Kg of phenol novolac epoxy resin, 15Kg of m-phenylenediamine and 80Kg of butanone to obtain the flame-retardant polyphenyl ether adhesive.
Example 5
A flame-retardant polyphenyl ether adhesive and a preparation method thereof comprise the following steps:
s1, adding 2mol of bisphenol A, 2mol of triethylamine and 50Kg of tetrahydrofuran into a round-bottom flask, uniformly stirring, then dropwise adding 1mol of hexachlorotriphosphazene dissolved in the tetrahydrofuran into the round-bottom flask, stirring at 25 ℃ for reaction for 18 hours, then dropwise adding 4mol of triethylamine and 4mol of methanol dissolved in the tetrahydrofuran into the round-bottom flask, continuing to react for 18 hours, filtering the reaction solution to obtain a filtrate, distilling under reduced pressure to remove a solvent, dissolving a crude product in chloroform, extracting with a saturated sodium chloride solution at room temperature to remove impurities, and distilling under reduced pressure to remove chloroform in an oil phase to obtain a phosphorus-containing bisphenol compound;
s2, adding 10Kg of polyphenyl ether, 2Kg of phosphorus-containing bisphenol compound and 40Kg of mesitylene into an autoclave, heating to 130 ℃ and stirring for dissolution, adding 0.5Kg of di-tert-butyl peroxide dissolved in the mesitylene into the reaction kettle within 3 hours, continuing to react for 6 hours, washing the reaction solution with sodium bicarbonate aqueous solution, and removing the mesitylene in the oil phase through reduced pressure distillation to obtain the low molecular weight polyphenyl ether;
s3, adding 10Kg of low molecular weight polyphenyl ether, 6Kg of biphenyl epoxy resin, 0.1Kg of 2-methylimidazole and 40Kg of mesitylene into a reactor, heating to 100 ℃ for reaction for 8 hours, and distilling under reduced pressure to remove a solvent to obtain low molecular weight epoxidized phosphorus-containing polyphenyl ether;
s4, uniformly mixing 100Kg of low molecular weight epoxidized phosphorus-containing polyphenyl ether, 60Kg of cresol novolac epoxy resin, 10Kg of dicyandiamide and 50Kg of toluene to obtain the flame-retardant polyphenyl ether adhesive.
TABLE 1 heat of taper and limiting oxygen index data for flame retardant polyolefin-based adhesive compositions and general polyolefin-based adhesive compositions
The data of the limiting oxygen index test of the flame-retardant polyphenyl ether adhesive prepared in the examples 1-5 and the common polyphenyl ether adhesive prepared in the comparative example 1 are compared, and the result shows that the limiting oxygen index of the flame-retardant polyphenyl ether adhesive is obviously higher than that of the common polyphenyl ether adhesive (27.6), and the flame retardant property of the flame-retardant polyphenyl ether adhesive is greatly improved. The foregoing is merely a preferred embodiment of the invention, and it is to be understood that the invention is not limited to the form disclosed herein but is not to be construed as excluding other embodiments, but is capable of numerous other combinations, modifications and environments and is capable of modifications within the scope of the inventive concept, either as taught or as a matter of routine skill or knowledge in the relevant art. And that modifications and variations which do not depart from the spirit and scope of the invention are intended to be within the scope of the appended claims.
Claims (9)
1. A preparation method of a flame-retardant polyphenyl ether adhesive is characterized by comprising the following steps: the method comprises the following steps:
s1, preparing a phosphorus-containing bisphenol compound;
mixing bisphenol A, triethylamine and tetrahydrofuran, dropwise adding hexachloro-triphosphazene dissolved in tetrahydrofuran after uniform stirring, dropwise adding triethylamine and methanol dissolved in tetrahydrofuran for continuous reaction after stirring reaction, filtering to obtain a crude product, and extracting and removing impurities from the crude product to obtain a phosphorus-containing bisphenol compound;
s2, preparing low molecular weight polyphenyl ether;
adding polyphenyl ether, phosphorus-containing bisphenol compound and mesitylene into an autoclave, heating to 80-100 ℃ and stirring for dissolution, then adding a free radical initiator for reaction, and washing and removing mesitylene from the reaction liquid after the reaction to prepare low-molecular-weight polyphenyl ether;
s3, preparing low molecular weight epoxidized phosphorus-containing polyphenyl ether;
mixing low molecular weight polyphenyl ether, an epoxy compound, a catalyst and mesitylene for high-temperature reaction to obtain low molecular weight epoxidized phosphorus-containing polyphenyl ether;
s4, uniformly mixing the low molecular weight epoxidized phosphorus-containing polyphenyl ether, epoxy resin, an epoxy resin curing agent and an organic solvent C to obtain the flame-retardant polyphenyl ether adhesive.
2. The method for preparing the flame-retardant polyphenyl ether adhesive as set forth in claim 1, wherein: in the step S2, the free radical initiator is one or more of tert-butyl hydroperoxide, benzoyl peroxide, dicumyl peroxide, lauroyl peroxide and di-tert-butyl peroxide.
3. The method for preparing the flame-retardant polyphenyl ether adhesive as set forth in claim 1, wherein: in the step S3, the epoxy compound is one or more of bisphenol a type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, alicyclic epoxy resin and biphenyl type epoxy resin.
4. The method for preparing the flame-retardant polyphenyl ether adhesive as set forth in claim 1, wherein: in the step S3, the catalyst is one or more of tetrabutylammonium chloride, tetramethyl ammonium bromide, tetraphenyl phosphine bromide, amyl triphenylphosphine bromide and 2-methylimidazole.
5. The method for preparing the flame-retardant polyphenyl ether adhesive as set forth in claim 1, wherein: the epoxy resin is one or more of tetraglycidyl diamino diphenyl methane, N, N, N' -tetraglycidyl m-xylene diamine, triglycidyl p-aminophenol, tetraglycidyl diamino methyl cyclohexanone, phenol novolac type epoxy resin and cresol novolac type epoxy resin.
6. The method for preparing the flame-retardant polyphenyl ether adhesive as set forth in claim 1, wherein: the epoxy resin curing agent is one or more of dicyandiamide, diaminodiphenyl methane, triethylamine and m-phenylenediamine.
7. The method for preparing the flame-retardant polyphenyl ether adhesive as set forth in claim 1, wherein: the organic solvent C is one or more of toluene, xylene, acetone and butanone.
8. A flame retardant polyphenylene ether adhesive prepared according to the method of claim 1, wherein: the polyphenyl ether adhesive is formed by mixing low-molecular-weight epoxidized phosphorus-containing polyphenyl ether, epoxy resin, an epoxy resin curing agent and an organic solvent C.
9. Use of the flame retardant polyphenylene ether adhesive according to claim 8, characterized in that: the polyphenyl ether adhesive is used for matrix resin for copper-clad plates.
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| TW498084B (en) * | 2000-07-19 | 2002-08-11 | Chang Chun Plastics Co Ltd | Flame-retardant resin and flame retardant composition containing the same |
| CN104263306B (en) * | 2014-09-26 | 2016-02-10 | 四川东材科技集团股份有限公司 | The preparation method of a kind of polyphenylene oxide sizing agent and copper-clad plate thereof |
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